JPH02255833A - Polyether copolymer, its production, production of powder of same, and polyether copolymer composition - Google Patents

Abstract

PURPOSE:To obtain a polyether copolymer having a high-MW and crystallizability and improved in heat resistance and mechanical strengths by copolymerizing a specified reaction product with a 4,4'-dihalogenobenzophenone. CONSTITUTION:A reaction product is obtained by reacting a dihalogenobenzonitrile (A) (e.g. 2,6-dichlorobenzonitrile) in an amount to give a weight ratio to the total of components A and E of 0.15-0.35 with a 4,4'- biphenol (B) in an amount equimolar to said total in the presence of an alkali metal compound (C) (e.g. K2CO3) in 200-2000 pts.wt., per 100 pts.wt. total of components (A)-(C), aprotic polar solvent (D) (e.g. N-methylpyrrolidone). This reaction product is copolymerized with a 4,4'-dihalogenobenzophenone (E) (e.g. 4,4'-dichlorobenzophenone) in an amount to give a molar ratio to said total of 0.65-0.85 at 150-380 deg.C to obtain the title copolymer having a melt viscosity (at 400 deg.C) >=3000, comprising repeating units of formulas I and II and having a compositional ratio of units of formula I of 0.15-0.35.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel polyether copolymer, a method for producing the same, a method for producing powder thereof, and a polyether copolymer composition. , a polyether copolymer that has crystallinity, exhibits sufficient heat resistance, and has excellent solvent resistance, mechanical strength, etc., and is useful as a material in the electric/electronic equipment field, mechanical field, etc.; A method for efficiently producing the polyether copolymer in a simple process, a method for producing a bulky powder of the polyether copolymer, and a method containing the polyether copolymer. , and a composition that further improves the excellent heat resistance and mechanical strength of this polyether copolymer.

[Prior art and problems to be solved by the invention] In recent years, engineering resins with various structures have been developed.
Although it is used in a wide range of fields such as precision machinery, OA equipment, and optical communication equipment, its performance has not yet been fully satisfied in all aspects, and the required performance has become more stringent. Because of this, the development of new materials is desired.

On the other hand, a polyether copolymer, which is one of these engineering resins, is a resin particularly excellent in heat resistance, and various proposals have been made regarding this polyether copolymer.

For example, in Japanese Patent Application Laid-open No. 47-14270,
A method for producing an aromatic bolier, -thyl copolymer has been proposed in which dinitrobenzonitrile, dihalogenobenzophenone, and dihydric phenol are reacted in the presence of an alkali metal compound.

However, according to this method, it is not possible to obtain a copolymer having a sufficiently high molecular weight, and the resulting copolymer cannot necessarily be said to have sufficient heat resistance or mechanical strength.

Moreover, in JP-A-60-235835, by simultaneously reacting diherogenobenzonitrile, 4,4'-dihalogenobenzophenone, and an alkali metal salt of a dihydric phenol, the following formula (a); A repeating unit represented by and the following formula (b).

(b) consists of repeating units represented by the above formula (however, Ar in the above formula is a divalent aromatic group), and the composition ratio of the repeating units represented by the above formula (a) is 0.5 or more Methods for producing polyether copolymers have been proposed.

However, the polyether copolymer in which the composition ratio of the repeating unit represented by formula (a) is 065 or more is amorphous and therefore maintains mechanical strength in a temperature range exceeding the glass transition temperature. Therefore, it is difficult to say that the heat resistance is sufficient.

On the other hand, in this method, if a raw material mixture corresponding to a copolymer with a composition ratio of repeating units represented by formula (a) is less than 0.5 is simultaneously copolymerized, a sufficiently high molecular weight polyether-based It is not possible to obtain polymers.

The present invention has been made based on the above circumstances.

The object of the present invention is to create a novel polyether copolymer which has crystallinity and exhibits extremely excellent heat resistance, has a sufficiently high molecular weight, has excellent mechanical strength, etc., and which is useful in combination with new materials. A method for efficiently producing this polyether copolymer, a method for producing bulky polyether copolymer powder, and a method for producing a bulky polyether copolymer powder containing this polyether copolymer. It is an object of the present invention to provide a composite material having further improved heat resistance, mechanical strength, etc., which are superior to those of an ether copolymer.

[First Step to Solve the Problem] To achieve the objective 1), the structure of the invention of claim 1 includes a repeating unit represented by the linear formula (■): (I) and the following formula (■): The composition ratio of repeating units represented by the above formula (1) is 0.15 to 0.35, and the melt viscosity at a temperature of 400 ° C. is 1.000 voids or more. 4IIjJ& of the invention of claim 2 has a molar ratio of 0.15 to 0.4° with respect to the total amount of dihalogenobenzonitrile and 4.4°-dihalogenobenzophenone. The reaction obtained after reacting an amount of dihalogenobenzonitrile corresponding to 35 with an equimolar amount of 4,4-biphenol to the above total amount in the presence of an alkali metal compound and a neutral polar solvent. The r-T nyl ratio is 0.65 to
The method for producing a polyether copolymer according to claim 1, characterized in that the copolymerization reaction is carried out with an amount of 4.4-dihalogenobenzophenone corresponding to 0.85, The composition of the invention is such that the molar ratio is 0.1 with respect to the total amount of dihalogenobenzonitrile, 4,4゛-dichlorobenzophenone, and 4.4゜-difluorobenzophenone.
dihalogenobenzonitrile in an amount corresponding to 5 to 0.35, and 4.4-biphenol and 4.4-dichlorobenzophenone in equimolar acids to the total amount, in the presence of an alkali metal compound and a neutral polar solvent. After reacting below,
2. The method for producing a polyether copolymer according to claim 1, further comprising carrying out a copolymerization reaction between the obtained reaction product and 4,4'-difluorobenzophenone.

The structure of the invention according to claim 4 is that the solvent is directly distilled off from the neutral polar solvent solution of the polyether copolymer produced by the method according to claim 2 or 3. A method for producing a polyether copolymer powder, the method comprising: producing a polyether copolymer powder; This is a composition formed by blending a polyether copolymer with a non-alcoholic filler.

Polyether copolymer One important point in the polyneedle copolymer according to claim 1 is that it consists of a repeating unit represented by the formula (I) and a repeating unit represented by the formula (II). In addition, the composition ratio of the repeating unit represented by the formula (I) is in the range of 15-0°35, and the composition ratio of the repeating units represented by the formula (I) is in the range of 15-0°35. 0
．． If it is less than 15, the glass transition temperature of the polyether copolymer will be low, resulting in a decrease in heat resistance, or the melting point will be high, leading to deterioration in moldability. On the other hand, if it exceeds 0.35, the crystallinity of the polyether copolymer will be lost and the heat resistance and solvent resistance will decrease.

Furthermore, it is important that the polyether copolymer of the present invention has a melt viscosity of 3.000 voids or less at a temperature of 400°C.

This is because a low molecular weight polyether copolymer having a melt viscosity of less than 3.000 voids cannot achieve sufficient heat resistance and mechanical strength.

The polyneedle copolymer of the present invention has, for example, a crystal melting point of about 330 to 400°C, has crystallinity, has a sufficiently high molecular weight, exhibits sufficient heat resistance, and has excellent solvent resistance and mechanical properties. It has excellent physical strength and can be suitably used as a new material in the electrical/electronic equipment field, mechanical field, etc.

1. Method for producing a polyether copolymer - Part 1 Claim 1
The polyether copolymer described in claim 2 is obtained by reacting dihalogenobenzonitrile and an alkali metal compound of 4,4°-biphenol in a specific usage ratio in the presence of a neutral polar solvent according to the method described in claim 2. After that, the reaction product can be produced by carrying out a copolymerization reaction with a specific amount of 4,4''-dihalogenobenzophenone.

In the method according to claim 2, specific examples of the dihalogenobenzonitrile used include, for example:
The following formula.

(However, in the formula, X is a halogen atom.) 2,6-dihalogenobenzonitrile represented by the following formula (However, in the formula, X has the same meaning as above.) 2, Examples include 4-dihalogenobenzonitrile.

Among these, preferred are 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and 2.4-dichlorobenzonitrile.
-dichlorobenzonitrile and 2,4-difluorobenzonitrile, particularly preferred are 2. It is todichlorobenzonitrile.

In the method of the present invention, the dihalogenobenzonitrile and 4,4'-biphenol represented by the following formula are reacted in the presence of an alkali metal compound and a neutral polar solvent.

The alkali metal compound to be used is
It may be any salt that can convert biphenol into an alkali metal salt, and there are no particular limitations, but alkali metal carbonates and alkali metal hydrogen carbonates are preferred.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include rubidium hydrogen carbonate and cesium hydrogen carbonate.

Among these, preferred are sodium hydrogen carbonate and potassium hydrogen carbonate.

In the method of the present invention, among the various alkali metal compounds mentioned above, sl-lium carbonate and potassium carbonate can be particularly preferably used.

Examples of the neutral polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N
-dimethylacetamide, N,N-diethylacetamide, M,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone,
Toethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-
Propyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, tomethyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N- Methyl-3,4,5-1-
2-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-
2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1
-oxosulfolane, l-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N, N.
-dimethylimidazolidinone, diphenyl sulfone, etc.

The proportion of the dihalogenobenzonitrile used is the molar ratio to the total amount of dihalogenobenzonitrile and 4,4゛-dihalogenobenzophenone, and the dihalogenobenzonitrile is usually 0.15-〇,]5. Preferably 0
．． The ratio of the alkali metal compound used is usually 1.01 to 2.50 equivalents, preferably 1.02 to 1.50 equivalents, per one hydroxyl group of the 4,4°-biphenol. The ratio is 20 wins.

Is there any particular restriction on the use of the neutral polar solvent? 2 Usually, the dihalogenobenzonitrile and the 4.
It is selected in the range of 200 to z,ooo parts by weight per 100 parts by weight of the total of 4°-biphenol and the alkali metal compound.

In the adhesive method of the present invention, the reaction product I & product obtained by reacting the dihalogenobenzonitrile with the 4,4'-biphenol in the presence of the alkali metal compound and the neutral polar solvent and the React with 4,4°-dihalogenobenzo-noenone.

The 4,4°-dihalogenobenzophenone to be used is a compound represented by the following formula: (wherein, X means the same as above), and in the method of the present invention, 4. 4'-
Difluorobenzophenone and 4,4°-dichloropenzophenone can be particularly preferably used.

In the method of the present invention, the 4,4'-dihalogenobenzophenone is a combination of 4,4'-dihalogenobenzophenone and dihalogenobenzonitrile, with ftM.

The molar ratio for using the 4.4-biphenol is usually 0.98 to 1.02, preferably 1.00 to
1. Use at a rate that makes it obsolete.

In order to obtain the polyneedle copolymer according to claim 1 by the production method of the present invention, for example, λ, the dihalogenobenzonitrile and the 4,4
゛-Biphenol and the alkali metal compound 1 are added simultaneously, and the dihalogenobenzonitrile and the 4 alkali metal compound are added simultaneously.
．． After the reaction of 4′-biphenol, the above-mentioned 4.4”-shiba r1 genobenzophenone is further added, and the temperature is usually 150 to 380°C, preferably 180 to 330°C.
A series of reactions are carried out at a temperature in the range of . If the reaction temperature is less than 150°C, the reaction rate is too slow to be practical.

If the temperature exceeds 380°C, side reactions may occur.

In addition, the reaction time of this series of reactions is usually 0.1 to 1
0 hours, preferably 1 hour to 5 hours.

After completion of the reaction, the polyether copolymer is separated and purified from the resulting neutral polar solvent solution containing the polyether copolymer according to a known method to obtain a polyether copolymer. I can do it.

In this way, the polyether copolymer according to claim 1 can be efficiently produced in a simple process.

-Production method of polyether copolymer-Part 2Claim 1
The polyether copolymer according to claim 3 is prepared by combining dihalogenobenzonitrile, 4,4'-dichlorobenzophenone, and 4,4°-biphenol in specific usage ratios, an alkali metal compound and The reaction product obtained by reacting in the presence of a neutral polar solvent and 4,4°-
It can also be produced by carrying out a copolymerization reaction with dichlorobenzophenone.

The dihalogenobenzonitrile, the 4,4'-dichlorobenzophenone, the 4,4'-difluorobenzophenone, the alkali metal compound, and the medium H polar solvent are as described in the method of claim 2. Similarly, there is ゛C.

In this method, the proportions of the dihalogenobenzonitrile and the alkali metal compound used are the same as those described in claim 2 above.

Further, the dihalogenobenzonitrile and the above 4.4. −
Dichlorobenzophenone and the above 4.4.-.

Total usage edge with difluorobenzophenone.

The molar ratio of the total usage value of 4.4"-dihalogenobenzophenone and dihalogenobenzonitrile to the amount of 4,4"-biphenol used is usually 0.98 to 1.L.
! , preferably 1. +) t', 01.

Then, the amount of 4,4゛-dichlorobenzophenone used in the -th stage reaction and the amount of 4,4゛-difluorobenzophenone used in the final polymer synthesis are 50
It is desirable to set the ratio to 95.5-40 (-1 nyl ratio).

The proportion of the alkali metal compound used and the amount of the neutral polar solvent used are the same as those explained in the method according to claim 2 above.

The reaction temperature, reaction time, etc. in this method are also the same as in the method according to claim 2 above.

Method for producing polyether copolymer powder By directly distilling off the solvent from the neutral polar solvent solution containing the polyether copolymer obtained by the production method according to claims 2 and 3 above. , produced a bulky polyneedle copolymer powder. I can do a lot of things.

The 7Afil temperature during distillation is usually 50 to 250°C, preferably 150 to 200°C, depending on the type of neutral polar solvent.

In addition, the distillation pressure fj during distillation is usually 5=75
0 rnrrii (g, preferably l mouth ~ 200 m
m ) (g.

When the solvent is directly distilled off in this manner, a polyether copolymer powder is obtained as a distillation residue, and this polyether copolymer powder can be subjected to ordinary purification operations.

The bulk density of the polyether copolymer powder obtained by this method is usually 0.3 to 0.6 g/Cmy.

If the bulk density is within the above range, the refining operation will be interrupted,
Improve productivity.

Note that the recovery rate of the neutral polar solvent during this solvent distillation is 95 to 9965%. In this respect as well, this method is a method with good solvent recovery efficiency.

-Polyether copolymer composition- Next, the excellent heat resistance and mechanical strength of the polyether copolymer according to claim 1 can be further enhanced in the composition according to claim 5. I can do it.

The composition according to claim 5 is obtained by blending the polyether copolymer according to claim Ip 1 and an S filler.

Examples of the inorganic filler include l&acid calcium,! Carbonates such as magnesium sulfate and dolomite: Sulfates such as calcium sulfate and magnesium sulfate; Sulfites such as calcium sulfite, talc, nitrate: mica; titania: zirco; nia; ferrite 1~: asbestos: glass fiber : Calcium silicate, montmorillonite) ~, bentoti 1 ~, etc.; silicate; iron, zinc [1, aluminum, nickel, etc.) metal powder, silicon carbide, silica nitride, boron nitride, and other ceramics; Whisker, Carbon Blauke, Graphai 1-1rRJ Mk male, etc.

These inorganic fillers may be used alone.
11 or two inserts may be used together.

In the present invention, the form of the inorganic filler is as follows:
There is no particular restriction, and the shape may be granular, plate-like, or male-like, especially if a fiber-like inorganic filler is used.
Significantly improves the elastic modulus of polyether copolymer compositions]
I can do it.

Further, the inorganic filler used has a particle size or an average fiber diameter of usually 20 mm or less.

A material having an optimum diameter may be appropriately selected depending on the purpose of containing the filler. Particle size or f average m of the inorganic filler! If the diameter of 11 is larger than 20jLnn, the dispersibility in the composition may be reduced.

Undeveloped [In Jl, the polyether copolymer ζ2
The blending ratio of the inorganic filler is usually 1 to 7.
The content is 0%, preferably 5 to 30%. If this blending ratio is less than 1% by weight, the heat resistance and mechanical strength of the composition may not be sufficient. On the other hand, if the amount exceeds 70% by weight, no improvement in the effect accompanying an increase in the blending ratio can be seen, and on the contrary, the moldability of the polyether copolymer composition may deteriorate.

The polyether copolymer composition of the present invention further improves the excellent heat resistance and mechanical strength of the polyether copolymer.

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) 32.34 ml of 2,6-cyclopenzonitrile is added to a reactor with a content of 851, equipped with a Dean-Starck trap filled with I-luene, a stirring device and an argon gas blowing tube.
g (0,188 mol), 4,4'-biphenol 1
39.65 g (0.75 mol), potassium carbonate 124
．． 39 g (0.9 mol) and N-medylvirolitone 1
．． 51 and heated to 195°C*T for 1 hour while blowing argon gas.

After the temperature reached 51°C, a small amount of toluene was added and the resulting water was removed azeotropically.

Next, the reaction was carried out at a temperature of 195°C for 30 minutes. After that, 122.85g of 4.4°-difluorobenzophenone was added.
A solution of (0,563 mol) dissolved in 1.5 ml of tomethylpyrrolidine was added, and the reaction was further carried out for 1 hour.

After the reaction is complete, transfer the product to a blender (manufactured by Warning)
Grind it with water, wash with acetone, methanol, water, and acetone in that order, and then dry it.

Copolymer 2 in white powder form with a bulk density of 0.12 g/cm1
5!1.36g (yield +98%) was obtained.

The properties of this polyether copolymer (melt viscosity (zero shear viscosity) at a temperature of 40 °C) were measured.
13.000 voids, glass transition temperature 182°C, crystal melting point 379°C, thermal decomposition start temperature 562'C (in air,
5% double weight loss).

Next, the degree of crystallinity of this polyether copolymer was measured from the scattering intensity using wide-angle X-rays, and was found to be 44%. In addition,
An attempt was made to measure the solution viscosity, but due to its high solvent resistance, it did not dissolve in any of the four organic solvents and could not be measured.

Further, when IR measurement was carried out, absorption due to nitrile group was observed at 2220 cm-' position, absorption due to carboxyl group was observed at 1650 cm-' position, and absorption due to carboxyl group was observed at 1240 eii-' position.
Absorption due to ether bond was confirmed at the ' position.

The polyether copolymer obtained from this result and the elemental analysis result is recognized to be composed of repeating units having the following structure.

In addition, the mechanical strength of test pieces obtained by injection molding this polyether copolymer was measured.

The results are shown in Table 1.

Note that the Jll determination for each evaluation item [1] was performed as follows.

Tensile strength, tensile modulus and elongation, according to AST D-638.

bending strength and Flexural modulus: Based on ASTM D790.

Eye full-impact strength, based on AST D-256.

Heat distortion temperature; Compliant with ASTW D-648.

Furthermore, when the solubility in various solvents was investigated using the same test piece as above, it was found to be insoluble in acetone, chloroform, carbon tetrachloride, methylene chloride, ethanol, toluene, and xylene. It is also insoluble in acids other than concentrated sulfuric acid, and in the case of concentrated sulfuric acid, the surface swells to some extent when immersed between the edges and the edges.

(Examples 2 to 5) In Example 1, except that the ratio of 2,6-cyclobenzonitrile and 4,4'-difluorobenzophenone used was changed to the ratio shown in Table 2.
It was carried out in the same manner.

The above formula (1) in the obtained polyether copolymer
Table 2 shows the proportion of repeating units represented by ; and the melt viscosity, thermal properties and crystallinity of the obtained polyether copolymer.

(Example 6) A polyether copolymer produced in the same manner as in Example 1 and an average diameter of several meters 1 (IL, average edge length 3a)
m glass fibers were kneaded in an extruder at a temperature of 360°C, extruded, and shredded to obtain pellets.

This bellet was injection molded to form a test piece.

The mechanical strength of the obtained test piece was measured.

The results are shown in Table 1.

(Example 7) A polyether copolymer produced in the same manner as in Example 1 and carbon fibers with an average fiber diameter of 9 units (Higashishikan, Trading Card T
300) were kneaded in an extruder at a temperature of 3110°C, extruded, and cut to obtain pellets.

This bellet was injection molded to form a test piece.

Measuring the mechanical strength of the obtained test piece1. Ta.

The results are shown in Table 1.

(Comparative Example 1) In Example 1 of the Imperial Rescript, 2. The charging ratio of todichlorobenzonitrile and 4,4°-difluorobenzophenone is
Polyether was prepared in the same manner as in Example 1, except that the molar ratio of (2, dichloropenzonitrile) and (4,4'-difluorobenzophenone) was changed from 25 to 5 to 10:9G. A copolymer was produced.

As a result, although a polyether copolymer was obtained,
This polyether copolymer had a low molecular weight and had a melt viscosity of 800 voids at 400°C.

Furthermore, the film obtained by press molding this polyether copolymer was extremely brittle.

(Comparative Example 2) In Example 1, 2. The charging ratio of todichlorobenzonitrile and 4,4゛-difluorobenzophenone is
The molar ratio of (2,6-cyclopenzonitrile):(4,4'-difluorobenzophenone) was changed from 25 to 5 to 40:60, and the reaction time was changed to 1.
．． A polyether copolymer was produced in the same manner as in Example 1 except that the heating time was changed from 5 hours to 1 hour.

As a result, the obtained polyether copolymer was 40
The melt viscosity at 0°C is 19.0°C, the viscosity is < the value measured at a temperature of 60°C using a 0.5g/di solution of p-chlorophenol, or 1.94dl.
The crystallinity was 7%, and it was almost amorphous.

Further, the glass transition temperature of this polyether-based copolymer was 195°C, and the thermal decomposition onset temperature was 542'C.

Next, the mechanical strength of a test piece obtained by injection molding this polyneedle copolymer was measured in the same manner as in Example 1 above.

The results are shown in Table 1.

Table 2 Note 1) Unable to measure due to melting (Example 8) 2. Todichlorobenzonitrile 30.962 g (0.18 mol), 4,4'-dichlorobenzophenone 75.333 g (0.30 mol)
, 4.4'-biphenol + 10゜609g (0,5
9 mol), potassium carbonate 120, :lag (0.72 mol) and N,N-dimethylimidazolidinone 3 were added and heated at 220°C for 1 hour while blowing argon gas.
The temperature rose to .

After increasing the temperature, a small amount of toluene was added to remove the resulting wood by azeotropy.

Next, after carrying out a reaction at a temperature of 220°C to 224°C for 2 hours, 4.4'-difluorobenzophenone 26°1
A solution of 84 g (0.12 mol) dissolved in 50 ml of N,N-dimethylimidazolidinone was added, and the reaction was further carried out for 1 hour.

After the reaction was completed, the same treatment as in Example 1 was carried out to obtain a white powdery polyether copolymer (191%, 27 g) (yield: 7%).
) was obtained.

Table 3 shows the results of measuring the properties of this polyether copolymer.

(Example 9) 38.702 g of 2,5-dichlorobenzonitrile (0,
225 mol), 4,4°-dichlorobenzophenone 94
．． 166 g (0,375 mol), 4,4°-biphenol: 18.354 g (0,743 mol), potassium carbonate 124.389 g (0,9 mol), 4,4'-difluorobenzophenone 32.73 g co, is mole)
The procedure was carried out in the same manner as in Example 8 except that white powder 250
．． 35 g (yield 98%) was obtained.

The results are shown in Table 3.

(Example 10) 2. Tojikuro a /(:/zonito!j le 23.221
g (0,135 mol'), 4.4'-dichlorobenzophenone S6.5 g (0,225 mol), 4.4
'-Biphenol 80.05g (0,441℃ mol),
Potassium carbonate 74°! i33g (0.54 mol), 4.
4°-difluorohenschiff x/”/19.6:
The same procedure as in Example 8 was carried out except that 1 gg (0,0' Jtl) was used, and 14 Jl of white powder was obtained. (Yield 9g%) was obtained.

The results are shown in Table 3.

(:J Example 11) 4.4゛-dichlorobenzophenone 82.866g (0
, 33 mol), 4,4'-difluorobenzophenone 19.6:18 g (0,0' 1 mol) was used in the same manner as in Example 8, and 250.31 g of white powder (yield 9%) was obtained. I got it.

Table 3 The results are shown in Table 3.

(Example 12) 90.4 g of 4.4"-dichlorobenzophenone (0,3
6 mol), 4,4'-difluorobenzophenone 1
3.092g (Example 8 except that 0°06 (nil) was used)
199.05g of white powder (yield 98%)
) was obtained.

The results are shown in Table 3.

(Example 13) 30 equipped with an argon gas blowing pipe, a distillation device, and a stirring device
0m! 6.303 g (0,025 mol) of 4゜4'-dichlorobenzophenone in a L separable flask, 2.6
- 2.580 g (0.015 mol) of cyclopenzonitrile, 9.207 g (0.05 mol) of 4,4°-biphenol
mol), potassium carbonate 8.293 g (fl, [)6-thyl), N,H''-imidazolidinone 25
After adding 0 m of mulberry and heating the inside of the flask to 220°C and maintaining this state for 2 hours, 2.182 g (mol of 4,4°-difluorobenzophenone) of 4,4°-difluorobenzophenone was added to H-dimethylimidazolidine. After the polymerization is completed, dissolve in 2 ml of non-alcoholic acid and add and heat to 220-223°C for an additional hour.
Immediately add 11 g of 600 mm at 200℃ while continuing to stir.
The solvent was distilled off over 1 minute. At the final stage of solvent distillation, 100-liter kneading was performed and pressure was applied.

The amount of solvent recovered was 911.5% at 246°C.

Polymer powder remains in the flask, and it is washed with water.
It was washed three times with water and once with acetone and dried.

Polymer yield Ji 16.8g (99% ”), glass transition temperature 185.2°C, melting point 376°C, thermal decomposition onset temperature 560°C (5% weight loss in air), melt viscosity at 480°C 26,000 voids. I was so excited.The bulk density was (1,51
z/cm'.

[Effect of the invention] (1) According to the invention of claim 1,! It is composed of specific repeating units with a specific ratio of 11 and exhibits a specific melt viscosity, and has a sufficiently high molecular weight, has solidity, and has sufficient heat resistance. In addition, it is possible to provide a novel polyether copolymer that has excellent mechanical strength, solvent resistance, etc., and is useful as a material in the fields of electricity, electronic equipment, machinery, etc.

(2) Also, according to the invention of claim 2 or claim 3,
A novel polyether copolymer having the above-mentioned excellent properties can be obtained efficiently through a simple process, and an industrially useful method for producing a borie-thyl copolymer can be provided. .

(g) According to the fourth aspect of the invention, it is possible to provide a method for producing a boether copolymer powder having a high bulk density.

(4) Furthermore, according to the invention of claim 5, the polyether copolymer of the invention of claim 1, which has excellent heat resistance and mechanical strength, has significantly improved heat resistance and mechanical strength. Useful new compositions can be provided.

Claims (5)

[Claims] (1) The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The repeating unit represented by (I) and the following formula (II); ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ Consists of repeating units represented by (II), and the composition ratio of the repeating units represented by formula (I) is 0.15 to 0.35
At the same time, the melt viscosity at a temperature of 400°C is 3,
A polyether copolymer characterized by having a poise of 000 poise or more. (2) 0.15 molar ratio to the total amount of dihalogenobenzonitrile and 4,4'-dihalogenobenzophenone
After reacting an amount of dihalogenobenzonitrile corresponding to ~0.35 with 4,4'-biphenol in an amount equimolar to the above total amount in the presence of an alkali metal compound and a neutral polar solvent, the obtained 4,4'- in an amount corresponding to a molar ratio of 0.65 to 0.85 with respect to the total amount of the reaction product and the above total amount.
2. The method for producing a polyether copolymer according to claim 1, which comprises carrying out a copolymerization reaction with dihalogenobenzophenone. (3) dihalogenobenzonitrile in an amount corresponding to a molar ratio of 0.15 to 0.35 with respect to the total amount of dihalogenobenzonitrile, 4,4′-dichlorobenzophenone, and 4,4′-difluorobenzophenone; After reacting 4,4'-biphenol and 4,4'-dichlorobenzophenone in an amount equivalent to the total amount in the presence of an alkali metal compound and a neutral polar solvent, the resulting reaction product and 4, The method for producing a polyether copolymer according to claim 1, characterized in that a copolymerization reaction with 4'-difluorobenzophenone is carried out. (4) A polyether copolymer, characterized in that the solvent is directly distilled off from the neutral polar solvent solution of the polyether copolymer obtained by the method according to claim 2 or 3. Method for producing polymer powder. (5) A composition comprising the polyether copolymer according to claim 1 and an inorganic filler.